Difficultly water-soluble anthraquinone dyestuffs

ABSTRACT

WHEREIN R1 represents hydrogen or lower alkyl, R3 represents hydrogen, lower alkyl, hydroxy-lower alkyl, alkenyl of at most four carbon atoms, cyclohexyl or benzyl, and R4 represents hydrogen, lower alkyl, hydroxy-lower alkyl or R3 and R4 taken together with the nitrogen atom to which they are linked, represent pyrrolidino, piperidino or morpholino, Z represents phenyl or phenyl monosubstituted by chlorine, bromine, fluorine, nitro, lower alkyl, lower alkoxy, hydroxylower alkyl, lower alkoxy-carbonyl, lower alkyl-sulfonyl or lower alkyl-sulfonyloxy, AND RING A bears no further substituents or is further monosubstituted by methyl, methoxy or chlorine, are particularly suited for the dyeing of hydrophobic organic fiber materials, especially polyethylene glycol terephthalate fibers but also other polyester fibers and synthetic polyamide and polyacrylonitrile fibers. The dyeings on polyethylene glycol terephthalate have great color strength and excellent fastness to sublimation and light. Dyestuffs free from salt-forming, water-solubilizing groups which dissociate acid in water which are of the formula

United States Patent [72] Inventors Hans Peter Kollllrer Munchenstein;Mario Christen, Reinach, both of Switzerland [21] Appl. No. 860,457 [22]Filed July 24, 1969 [45] Patented Nov. 23, 1971 [73] Assignee Ciba-GeigyAG Basel, Switzerland [32] Priority Feb. 25, 1966 [33] Switzerland [312771/66 Original application Feb. 20, 1967, Ser. No. 617,060, now PatentNo. 3,541,182. Divided and this application July 24, 1969, Ser. No.860,457

[54] DIFFICULTLY WATER-SOLUBLE ANTHRAQUINONE DYESTUFFS 8 Claims, NoDrawings [52] US. Cl 260/152, 8/4, 8/41 R, 8/41 A, 8/41 B, 8/41 C, 8/50,117/1388 R, 1 17/1388 D, 117/138,8 F, 117/144, 260/144, 260/155,260/156, 260/157, 260/158, 260/ 162, 260/163, 260/165, 260/205, 260/206,260/207, 2601207. 1 260/208, 260/376 51 1 Int. Cl C09b 1/42, C09b 29/08,C09b 43/12 [50] Field of Search 260/162, 152,156,157,l58,165, 207, 207.1

[ 56] References Cited UN lTED STATES PATENTS 2,108,126 2/1938 Honold etal 260/207.l X 2,228,455 l/l94l Honold et a1 260/207.1 2,559,667 7/1951Schroeder et al 260/207.1

2,779,772 l/l957 Frey 260/207.1X 2,957,884 10/1960 Moergli 260/207.1UX

Primary ExaminerFloyd D. Higel Almrneywenderoth, Lind & Ponack ABSTRACT:Dyestuffs free from salt-forming, water-solubilizing groups whichdissociate acid in water which are of the formula N=N- Z 11 wherein R,represents hydrogen or lower alkyl,

R represents hydrogen, lower alkyl, hydroxy-lower alkyl, a1 kenyl of atmost four carbon atoms, cyclohexyl or benzyl, and R represents hydrogen,lower alkyl, hydroxy-lower alkyl or R and R taken together with thenitrogen atom to which they are linked, represent pyrrolidino,piperidino or morpholino,

Z represents phenyl or phenyl monosubstituted by chlorine, bromine,fluorine, nitro, lower alkyl, lower alkoxy, hydroxylower alkyl, loweralkoxy-carbonyl, lower alkyl-sulfonyl or lower alkyl-sulfonyloxy,

and ring A bears no further substituents or is further monosubstitutedby methyl, methoxy or chlorine. are particularly suited for the dyeingof hydrophobic organic fiber materials. especially polyethylene glycolterephthalate fibers but also other polyester fibers and syntheticpolyamide and polyacrylonitrile fibers. The dyeings on polyethyleneglycol terephthalate have great color strength and excellent fastness tosublimation and light.

DIFFICULTLY WATER-SOLUBLE ANTHRAQUINONE DYESTUFFS NH-Rr l wherein R,represents hydrogen or a lower alkyl group,

X represents the radical of an organic hydroxyl compound bound by way ofan oxygen, or a primary, secondary or tertiary amino group,

Y represents a mobile substituent enabling nucleophilic substitution,

with an amine of formula ll 2 represents an optionally substitutedcarbocyclic-aromatic or heterocyclic-aromatic radical, and the benzenering A can have other substituents, preferably such that do notdissociate acid in water, to form a compound of formula Ill wherein R,and X have the meanings given for formula l and Z and A have those givenfor formula ll. The starting compounds are to be so chosen that thefinal dyestuff does not contain any salt-forming, water-solubilizinggroups which dissociate acid in water such as sulfonic acid, carboxylicacid or phosphonic acid groups.

As lower alkyl group, R, represents, e.g., isopropyl, ethyl and,especially, methyl; preferably however, R, is hydrogen.

As radical of an organic hydroxyl compound bound by way of oxygen, Xrepresents, for instance, the group OR, wherein R is an optionallysubstituted aliphatic, cycloaliphatic, carbocyclic-aromatic orheterocyclic-aromatic radical.

When X is a primary, secondary or tertiary amino group, then it is,particularly, a group of the formula (III) optionally substitutedaliphatic or cycloaliphatic radical, or R:,

and R, together with the nitrogen atom to which they are linkedrepresent, optionally with the inclusion of another heteroatom, a fiveorsix-membered heterocyclic ring.

Accordingly, the dyestuffs according to the invention constitute twosubclasses, one in which the 2-position of the anthraquinone nucleus issubstituted by an esterified carboxyl group of the formula -co-oR,

and another subclass in which the aforesaid 2-position is occupied by anamidified carboxyl group of the formula R-,R and R, having the meaningsgiven above.

The dyestuffs of the first-mentioned subclass afford dyeings onhydrophobic fibers which are generally of greater lightfastness thanthose obtained with dyestuffs of the second subclass.

In each of these subclasses, the dyestuffs in which 2 represents anoptionally substituted monoor dinuclear carbocyclic aromatic radical aremore important because they are easier to produce than those in which Zis a heterocyclic radical.

When R R and R, represent aliphatic radicals these are, e.g., straightor branched chain, optionally substituted alkyl or alkenyl groups, andin the latter case, particularly A2-alkenyl groups, having preferably upto five carbon atoms. As substituents, these aliphatic radicals cancontain, e.g., hydroxyl or preferably alkoxy groups, such asunsubstituted all-toxy, alkoxyalkoxy or alkoxyalkoxyalkoxy groups, oralltoxycarbonyl groups, wherein the alkoxy moiety has from one to threecarbon atoms. As substituents, they can also contain carbocyclic rings,especially of aromatic character, such as the phenyl radical, orheterocyclic rings, such as the thienyl-(Z), furyl-(Z) ortetrahydrofuryl-(2) radical.

Cycloaliphatic radicals symbolized by R,R, and R, are, e.g.,

cycloalkyl groups with preferably fiveor six-membered rings and,especially, the cyclohexyl or methylcyclohexyl group.

As carbocyclic-aromatic radicals represented by R, and R mononuclearsubstituents of the benzene series are preferred, especially anunsubstituted phenyl group or a phenyl group substituted by at least oneand preferably not more than three of the following substituents: nitro,chlorine, bromine, fluorine, alkyl, alkoxy, and/or one of thesubstituents hydroxy-alkyl, alkoxy-carbonyl, alkyl-sulfonyl oralkyl-sulfonyloxy, alkyl and alkoxy" portions having at most four carbonatoms.

lf R and R represent heterocyclic-aromatic radicals, then these arepreferably fiveto six-membered cyclic radicals, especiallynitrogen-containing rings of aromatic character, e.g., pyridineradicals, more particularly the pyridyl-(3) radi cal.

When R, and R, together with the nitrogen atom to which they are linkedrepresent a fiveor six-membered heterocyclic ring, then this is, e.g.,the pyrrolidino, piperidino, piperazino, thiomorpholino or, especially,the morpholino ring.

Dyestuffs falling under formula lll in which R, represents an alkylradical having at most three carbon atoms or such an alkyl radicalsubstituted by alkoxy, alkoxyalkoxy or alkoxyalkoxyalkoxy groups havingfrom one to three carbon atoms per alkoxy portion, or in which each ofR, and R, represent an alkyl group having at most three carbon atoms,have particularly good drawing power onto organic hydrophobic fibers andgood fastness to sublimation and to light.

When 2 is a carbocyclic-aromatic radical, then it is, e.g., a naphthylor preferably a mononuclear residue of the benzene series.

When Z is a heterocyclic-aromatic radical, then it is for example anazolyl radical which can be condensed, particularly with a benzenenucleus. Examples are 2-lower alkyl-indolyl- (3) radicals, the diazolylradicals such as pyrazolyl radicals, e.g., l-lower alkyl-pyrazolyl-(S)or l-phenyl-3-lower alkyl-S- hydroxypyrazolyl-(4) radicals, l-loweralkyl-indazolyl-(Zi) radicals or imidazolyl radicals, e.g.,benzimidazolyl-(Z) radicals, or the ethiazolyl radicals such asthiazolyl-(Z) or benzothiazolyl-(Z) radicals. Also azinyl groups, e.g.,pyridyl groups such as the pyridyl-(3) group can be in the position ofZ.

The carbocyclic-aromatic rings in X and 2 as well as the benzene ring Acan contain other substituents which do not dissociate acid in water,rendering the dyestuffs water soluble, and do not elongate the resonancesystem, hence not detrimentallyfiecting the purity of the shade of thedyestuffs? suitable substituents are especially halogen, e.g., fluorine,chlorine or bromine, nitro, lower alkyl, hydroxy-lower alkyl, loweralkoxy, but also lower alkoxy-carbonyl, lower alkyl-sulfonyl or loweralkyl-sulfonyloxy groups.

In this specification, including the claims, the term lower applied toalkyl and alkoxy" means such groups having one to five carbon atoms.

In preferred dyestufi's falling under formula III, which are by gooddrawing power and fastness to sublimation and light, R, representshydrogen, lower alkyl, hydroxylower alkyl, alkenyl of at most fourcarbon atoms, cyclohexyl or benzyl, and R represents hydrogen, loweralkyl hydroxylower alkyl, or R, and R taken together with the nitrogenatom to which they are linked, represent pyrrolidino, piperidino ormorpholino, Z represents phenyl or a phenyl group monosubstituted bychlorine, bromine, fluorine, nitro,

lower alkyl, lower alkoxy, hydroxy-lower alkyl, lower-alltoxycarbonyl,lower-alkyl-sulfonyl or lower-alkyl-sulfonyloxy. Ring A in thesepreferred dyestuffs is either without additional substituents apart fromthe grouping N=NZ, or it is monosubstituted by methyl, methoxy orchlorine.

Most preferred are those of the above class of dyestuffs falling underformula III in which 2 represents phenyl or methylphenyl and in which R,and R, represent hydrogen or, more preferably, lower alkyl, or R, and R,taken together with the nitrogen atom to which they are linked representpiperidino or morpholino.

in the most preferred dyestuffs, the ring A is either without furthersubstitution or bears one methyl group.

In the starting compounds of formula I, Y, as mobile substituentenabling nucleophilic substitution, represents e.g., halogen such aschlorine or bromine, a lower alkoxy group such as the methoxy or ethoxygroup, the hydroxyl or the nitro group. Preferably, however, Y isbromine, or also chlorine.

Some of the starting materials of formula I are known or can be producedby methods known per se, e.g., by converting ananthraquinone-2-carboxylic acid of the formula i) NIH-R1 COOH into itsxylic acid "at 'biaaiiaeana reacting the" amino-Z-carbophenoxyt-chloroor-4-bromo-anthraquin-- one, l-amino-2-carbo-(pyridyloxy)-4-chloro or-4-bromoanthraquinone, l-amino-4-chloroor.-4-bromo-anthraquinone-2-carboxylic' acid amide, -2-carboxylicacid-N-alkylamides, -2-carboxylies acid-N-cyclo-alkylamides,-2-earboxylic acidNJl-dialkylamides, -2-carboxylicacid-N-hydroxyalkylamides, -2-carboxylicacid-N,N-bis-hydroxyalkylamides, -2- carboxylicacid-N-alkyl-N-arylamides, -2-carboxylic acid-N- pyridylamide,-2-carboxylic acid-N-alkyl-N-phenalkylamides or -2-carboxylic acidpiperidide or morpholide, as well as the corresponding l-methylaminoanalogues.

The greater part of the aminoazo compounds of formula ll which can beused as starting material are also known, or they can be produced by theusual methods by coupling diazotized nitroanilines or acylamino anilineswith coupling components and subsequent reduction of the nitro group orhydrolysis of the acylamino group to the amino group.

The condensation of starting materials of fonnula l with the amines offormula II is performed, e.g. with an excess of amine in a melt at70-250 C. it is preferably performed, however, in an inert organicsolvent at reaction temperatures of l00-l60 C. in the presence of anacid binding agent and a catalyst.

FoTnat ic hydrocarbons such as toluene or xylenes, halogenated aromatichydrocarbons such as chlorobenzene or dichlorobenunes, or nitratedaromatic hydrocarbons such as nitrobenzene can be used, for example, asinert organic solvents. Alcohols are particularly suitable, especiallyalkanols having at least two carbon atoms, e.g. ethanol, norisopropanol, butanols or amyl alcohols, 'or alkylene glycols and theirmonoalkyl ethers, e.g. ethylene glycol and its monomethyl or monoethylether.

Alkali metal hydroxides, particularly sodium or potassium hydroxides,alkali metal carbonates, especially sodium or potassium carbonate andalkali metal salts of lower fatty acids such as alkali metal acetatesare mentioned as preferred acid binding agents.

Copper or copper-(I) salts such as copper-(l) acetate or chloride arementioned as preferred catalysts.

A modification of the process according to the invention for theproduction of new, difficulty water-soluble anthraquinone dyestuffs offormula III consists in condensing an anthraquinone compound of formula1V NH-Rr CO-Hal wherein X has the meaning given for fonnula I, to form acompound of formula III, the components being so chosen that the finaldyestuff contains no salt-forming, water-solubilizing groups withdissociate acid in water.

The anthraquinone compound of formula IV is obtained, e.g. by reactingthe corresponding anthraquinone-Z-carboxylic acid with a halogenatingagent such as thionyl chloride or phosphorus pentachloride by usualmethods.

The condensation of the anthraquinone compound of formula IV with thecompound of formula V is performed in a known way, advantageously in aninert organic solvent, e.g. in an aromatic hydrocarbon, halogenated ornitrated hydrocarbon or in water and, optionally, in the presence ofacidbinding agents.

A second modification of the process according to the invention for theproduction of compounds of formula III wherein R,is hydrogen consists inreducing an anthraquinone compound of formula VI wherein X has themeaning given for formula 1, and Z and A have those given for formulall, the components being so chosen that the end product obtained doesnot contain any salt-forming, water-solubilizing groups which dissociateacid in water.

The reduction is advantageously performed with watersoluble sulfides orhydrogen sulfides in aqueous dispersion or in aqueous-organic solutionor dispersion. The organic part of such mixtures preferably consists ofwater-miscible, inert, organic solvents such as tertiary nitrogen bases,e.g. pyridine or homologues thereof, or it consists of amides of lowfatty acids such as N,N-dimethyl fonnamide, or of aliphatic alcoholse.g. alkylene glycol monoalkyl ethers, for example ethylene glycolmonomethyl or monoethyl ether.

A third modification of the process according to the invention for theproduction of new, difficulty water-soluble anthraquinone dyestuffs offormula III consists in condensing an anthraquinone compound of formulaVll wherein X and Y have the meanings given in Formula I, and Z and Ahave those given for formula II, with an amine of formula VH1 (VII) withan aminoazo compound of the formula wherein A, X, Y and Z have themeanings given above.

A further modification of the process according to the invention for theproduction of anthraquinone dyestuffs of formula III wherein Xrepresents a primary, secondary or tertiary amino group, consists incondensing an anthraquinone compound of formula IX with ammonia or aprimary or secondary amine and, if Q is a nitro group, reducing saidnitro group simultaneously to the amino group NH,, the startingcompounds being so chosen that the end product obtained does not containany salt-forming, water-solubilizing groups with dissociate acid inwater.

The conversion of the esters of formula lX into the corresponding amidesand optional reduction of the nitro group are carried out, preferably inan excess of ammonia or amines, and, optionally, in the presence ofinert organic solvents such as given above for the other processes.

When producing the new anthraquinone dyestuffs of formula lll, theygenerally precipitate from the reaction mixture or they can beprecipitated from the reaction mixture by the addition of water or ofwater-miscible, inert organic solvents, e.g. lower alkanols. In the purestate, they are shimmering deeply colored, crystalline substances.

Advantageously, the dyestuffs according to the invention are broughtinto a finely distributed form by milling with dispersing agents. Forthis purpose, anionic dispersing agents, e.g. alkyl-aryl sulfonates,condensation products of formaldehyde and naphthalene sulfonic acids,lignin sulfonates, or nonionogenic dispersing agents such as fattyalcohol or higher alkylphenol polyglycol ethers are suitable. Thedyestufis according to the invention are preferably milled with suchdispersing agents with the addition of water. The resultant, aqueousdyestuff pastes which contain the dyestuffs in finely distributed formcan either be used direct for dyeing or they can be formulated intonondusty powders by careful drying according to known methods.

In such preparations, the dyestuffs according to the invention aresuitable for the dyeing of organic material, particularly of hydrophobicorganic fiber material, from an aqueous dispersion, e.g. for the dyeingof cellulose ester fibers such as cellulose di-, 2%-tri-acetate,preferably however, they are suitable for the dyeing of textile fibersmade from polyesters of aromatic polycarboxylic acid with polyvalentalcohols such as polyglycol terephthalate, polyglycol isophthalate orpolycyclohexane diol terephthalate fibers.

The dyestuffs can also be used, however, for dyeing of syntheticpolyamide fibers such as polyamide 6, 66 or 1 l In some cases, alsovaluable dyeings can be attained with the dyestuffs according to theinvention polyacrylonitrile fibers.

Polyglycol terephthalate fibers are dyed with aqueous dispersions ofdyestufis according to the invention, for example, at temperatures ofover C. under pressure. Dyeing can also be performed, however, at theboiling point of the dye liquor in the presence of carriers, e.g. alkaliphenyl phenolates such as sodium-o-phenyl phenolate, polychlorobenzenecompounds or similar auxiliaries. Very good dyeings are also obtained ifthese fibers are impregnated with concentrated aqueous dispersion ofdyestuffs according to the invention, then squeezed out, dried and thedyestuffs are finally fixed at temperatures of 100 -250 C. In manycases, the drawing power of the dyestuffs onto these fibers and thestability of the aqueous dispersions in the dye liquor can be improvedby mixing two or more dyestufl's of similar composition of which atleast one is embraced by formula III.

Compared with corresponding dyeings attained with known green dyestuffsof similar constitution under the same conditions, the green dyeingsattained with the dyestuffs according to the invention on hydrophobicpolyester fiber material, particularly polyglycol terephthalate fibers,having a substantially greater color strength and/or fastness tosublimation and to light. The color strength may be improved as much as50 to 100 percent. Moreover, vegetable and animal fibers, particularlycotton, are well reserved by the dyestuffs according to the invention.Another advantage of the dyestuffs according Coloration of the organicmaterials is effected in either case i by penetration of dyestuffmolecules into the organic material, especially the fibers, and partialreagglomeration to larger dyestuff particles in the interior of thefibers.

The following nonlimitative examples illustrate the invention further.The temperatures are given therein in degrees Centigrade. Percentagesare given by weight.

Example I 26 g. of l-amino-2-carbomethoxy-4-bromoanthraquinone, 59 g. of4-aminoazobenzene, 22.1 g. of anhydrous potassium acetate and l g. ofcopper-(l) chloride are added to 100 g. of amyl alcohol, in the reactionmixture is stirred until homogeneity is attained and kept for 10 hoursat l30-l 35. The reaction mixture, which has become yellow-greencolored, is then cooled to 90', 200 g. of ethanol are added and then itis stirred for another 3-4 hours at room temperature.

The dyestuff of the above formula precipitates as a dark greygreencrystalline powder. This is separated by filtration, washed, dried andrecrystallized to further purify from ethylene glycol monomethyl ether.

COOCH;

From aqueous dispersion, the new dyestuff dyes polyethylene glycolterephthalate fiber material in clear green shades which have very goodfastness to light and sublimation.

if, instead of the 36 g. of l-amino-2-carbomethoxy-4-bromoanthraquinone, equimolar amounts of one of the anthraquinonecompounds given in the following table, columns l and ii, are used andif, instead of the 59 g. of 4- aminoazobenzene, equimolar amounts of oneof the aminoazo compounds given in column 11] of the same table areused, then with otherwise the same procedure as given in the example,dyestuffs are obtained which dye polyglycol terephthalate fiber materialin the shades given in column IV of this table. The dyeings are alsofast to light and sublimation.

TABLE Anthraquinone compound (f NH-Rr -C O-X Shade of dyleln on] O y your 0 m rthal- Number NH-R| C0-X Aminoazo compound ate bros 2 NH; O O O 011; Green.

' NHg- N=N 3 NH| Same as above Cl D0- 4 NHa -.do OCH; 0-

NHz -N=NC memoir 5 -NH: .(10 CH; 0-

NHQN=NQCH1CH2OH 6 NHCH do D0.

NHz- N=N 7 NH2 COOCHzCHzOCH NH, N=N

8 NH2 Same as above C NH N =N- 9 -NH -cooomcmon 0H3 NH N= Anthraquinonecompound (I) NEG-R1 Shade of l dyein on 0 Br I polyg ycol terephthal-Number --NHR1 0 0-K Aminoazo compound ate fibres 21 '-ooocfi;cmon,o

Do NHT- -1-I=N- 22 NH2 CO0C5H 1 CH S D0 NHg- N=NC\\\ 23 NHC; HCO0CHzCHzOCH D0.

NHz-

* 24 -NH2 DO.

-c00 CH NH 25 NH2 CO(O CHzCHghOCH; D0.

NHg- N=N 26 -NH: Same as above D0.

-COOOHIU -NH: -COOCH(CH;)2 D0. NH2 CH; D0.

CO 0 CH 29 -NH1 cooc(om)a -do Do.

30 -NHz 01H; Do.

NH N=N C O O C (011:)2

31 NH2 N Same as above D0- NH -c0ocH,-cH= cH, Mao o; Do. NH2 -COOC2H5D0.

NHz- N=N-- N02 34 NH2 Same as above D0.

NHz- N=N.

l CH3 35 -NH2 COOCHOHOCH; D0.

NH N=N- as NH1 -0 0 0 0112011930 0,115 Do.

NHz- N=N- 31 NH: -coocmomcmocm Do.

NH. N=N Br 38 -NH: COOCH D0.

NH N=N F 39 NH; CH D0. NH N=N- C O 0 CH CHzOCHa 40 -NH= /CH; Same asabove Do.

--C O O CH C O O czHs 41 -NH2 COOCH5 D0.

C 0-0 0-8 Oz-CH,

Anthraquinone compound (1 1 lIHR1 ShadB of II dyeing on 0 Br polyglycoltare hthal- Number -NHR 0 0-K Aminoazo compound ate bres so NH; Do.

0 0NH NHz- N=N 61 -NH: -O O NHCH -CH=CH Same as above D 62 NH2 -..do Do.

0 O0-- CH;

63 "NHZ CH3 CH3 D0.

64 -NHz OCH; Do.

65 NH: N 02 DO.

66 NHCH; Do.

-C 0-0 01 NHz- N=N CHzC H1O II 67 NH: Same as above D0.

68 NH: 01 ..do Do.

69 NH: Cl v.. d0 Do.

--0 o-o-C c1 C1 10 NH1 F ..do .j Do.

71 -NH2 D0.

C 0-0 CHzCHzOH NH -N=N(||J(|3CH HO N 12 -NH, Do.

U O0 COOCH; NHg- N=N 72a NH: C 0-0 CzH; Do.

NH N=N 73 -NH: S OzCzHg D0.

NH- N=N 74 NH Same as above Do.

l02 g. of 4-( l -phenyl-3'-methyl-5'-hydroxy)-pyrazolyl-(4'- azo)- l-aminobenzene, 37.3 g. of l-amino-4- bromoanthraquinone-2-carboxylicacid-N,N-dimethylamide, 25 g. of anhydrous potassium acetate and l g. ofcopper-(l) acetate in 200 g. of ethylene glycol monoethyl ether arestirred for IS hours at l30-l 35 and then 150 g. of methanol are addedat 80. The reaction product of the above formula precipitates in afinely crystalline form. It is separated by filtration, washed, driedand recrystallized from pyridine.

After developing at about 200 on polyglycol terephthalate fabric whichhas been impregnated with the aqueous dispersion of this,dyestuff andthen dried, a deep green dyeing having excellent fastness to light andsublimation is obtained.

Example 76 fl) NH:

C ONH:

34.5 g. of l-amino-4-bromoanthraquinone-2-carboxylic acid amide, 90 g.of 4-amino-4'-methoxyazobenzene, g. of sodium bicarbonate and 1.6 g. ofcopper-(I) acetate in I50 g. of isoamyl alcohol are stirred for 8 hoursat l-l30. 100 g. of ethanol are then added to the reaction mixture; itis cooled to room temperature whereupon the condensation product of theabove formula precipitates. It is separated by filtration, washed anddried.

The new dyestufi draws from aqueous dispersion onto polyglycolterephthalate or cellulose triacetate fabric in clear green shades whichhave very good fastness to sublimation.

Example 77 COOCHa 31.6 g. ofl-amino-2-carbomethoxy-4-chloroanthraquinone, 67.5 g. of4-amino-3,2'-dimethyl-azobenzene, 22.1 g. of anhydrous potassium acetateand l g. of copper-(l) chloride in 120 g. of n-butanol are stirred for24 hours at ll5-l 20, the reaction mixture is cooled to room temperatureand 180 g. of methanol are added. The dyestuff of the above formulaprecipitates from the solution in finely crystalline fonn. It isseparated by filtration, washed and dried.

The dyestufi obtained is mixed in a weight ratio of 1:1 with thedyestuff obtained according to example I. The mixture is milled withsand to attain a fine distribution and dispersed in a condensationproduct of naphthalene sulfonic acids and formaldehyde. From thisdispersion the dyestufi' mixture draws onto polyglycol terephthalatefiber material in vivid green shades which are fast to wet, light and,particularly, sublimation.

Example 78 0 NH CH:

COOCH;

54.4 g. of condensation product ofl-chloro-Z-carbornethoxy-4-bromoanthraquinone and 4-amino-2'-rnethyl-4'-chloroazobenzene are stirred for 5 hours at 35-40 in 200 g. of a 35percent aqueous solution of methylamine. The reaction mixture is cooledto l0-l 5 the reaction product formed of the above formula is separatedby filtration, washed with water until the reaction is neutral anddried. The dyestuff obtained dyes polyglycol terephthalate fabric froman aqueous dispersion by the thermosol process in clear green shadeswhich have excellent fastness to wet, sublimation and light.

Example 79 O NR2 C ONH:

" Q Q 0 NH N=N 52 g. ofl-nitro-2-carbethoxy-4-(4'-phenylazo-phenylamino)-anthraquinone-phenylazo-phenylamino) are slurried in 500 ml. of ethanol. A stream ofammonia is introduced for half an hour into this dispersion untilsaturation is attained whereupon the dispersion is heated to 60-70 in asteel autoclave while stirring or shaking. At l5-minute intervals, theammonia used up by the reaction is replaced by application of ammoniafrom a steel cylinder in such a manner that the pressure in the reactionvessel remains constant. The reaction mixture is then kept for anotherhour at thk temperature and cooled to room temperature, whereupon theobtained residue is filtered off, washed with water until the reactionis neutral and then dried.

The dyestuff is dark grey-blue crystalline powder. I! dyes polyglycolterephthalate fibers from an aqueous dispersion in clear green shadeswhich have excellent light and sublimation fastness.

The same dyestufi' is obtained if instead of 52 g. of l-nitro-2-carbethoxy-4-(4-phenylazo-phenylamino)-anthraquinone, 49.2 g. ofl-amino2-carbethoxy-4-(4'-phenylazo -phenylamino)-anthraquinone or 49.3g. of l-nitro-2-carbamyl-4- (4'-phenylazo-phenylamino)-anthraquinone areused as starting materials and otherwise the condensation is carried outas described above.

Example 80 I NH2 ll iH HQ 16 g. of 70 percent sodium hydrogen sulfideare added at 85-90 to the partial solution of 52 g. ofl-nitro-2-carbethoxy-4-(4'-phenylazo-phenylamino)-ant.hraquinone in 300g. of 50 percent aqueous pyridine and the reaction mixture is thenstirred for 10 minutes at this temperature. The blue-green dispersionformed is diluted with 300 ml. of water, cooled to room temperature andthe reaction product is separated by filtration, washed and dried. Thedyestuff obtained dyes polyglycol terephthalate fibers from an aqueousdispersion in clear green shades which have excellent and sublimationfastness.

Example 81 34.6 g. of 1-amino-4-brornoanthraquinone-Z-carboxylic acid,59.1 g. of S-aminoazobenzene, 22.1 g. of anhydrous potassium acetate and0.8 g. of copper powder are stirred in 115 g. of n-amyl alcohol for 20hours at ll-l20". 60 g. of methanol are then added to the reactionmixture which is then cooled to room temperature whereupon thecondensation product precipitates. This is dissolved in 5 percent sodiumbicarbonate solution filtered to clarify, the filtrate is acidified withpercent hydrochloric acid and the precipitated product is separated byfiltration, washed and dried.

37.0 g. of the condensation product so obtained are boiled in 250 g. ofthionyl chloride for 5 hours. The excess thionyl chloride is thenremoved in vacuo, the residue is taken up in 200 g. of o-dichlorobenzeneand, after the addition of 67 g. of anhydrous methanol, the whole isstirred for 6 hours at 8090 The reaction mixtures is then cooled to 0-l0whereupon the reaction product of the above formula crystallizes out ina very pure form. It is filtered ofl, washed and dried. Polyglycolterephthalate fabric is dyed from an aqueous dispersion of the dyestuffso obtained in pure green shades which have excellent sublimation andwet fastness properties.

Example 82 2 g. of the mixture of dyestuffs described in example 4 aredispersed in 4,000 ml. of water which contains l2 g. of sodiuin-o-phenylphenolate and l2 g. of diammonium phosphate, and 100 g. of a polyglycolterephthalate fabric are introduced into the dyebath. Dyeing isperformed for 1% hours at 95-98 The fabric is' then rinsed andthoroughly washed with dilute sodium hydroxide solution and acondensation product of napthalene sulfonic acids and formaldehyde. Agreen dyeing which is fast to sublimation, light and wet is obtained.

Example 83 2 g. of the finely milled dyestuff obtained according toexample l are dispersed in 4,000 ml. of water which contains 2 g. of acondensation product of naphthalene .sulfonic acids and formaldehyde.The pH of the dyebath is adjusted to 6.5 with acetic acid. 100 g. ofpolyglycol terephthalate fabric are introduced into the dyebath at 40,the bath is heated within l5 minutes to 120 in a closed vessel and iskept for 45 minutes at this temperature. The fabric is then rinsed withwater and subsequently soaped. In this way a clear, green dyeing isobtained which has excellent fastness to sublimation, wet and light.

Example 84 Polyglycol terephthalate fabric is impregnated in a foulardat 40 with a liquor of the following composition.

30 g. of dyestufi' according to example 80, finely dispersed 7.5 g. ofsodium alginate 10 g. of condensation product of formaldehyde andnaphthalene sulfonic acids and 950 g. of water.

The fabric which has been squeezed out to a liquor content of aboutpercent (calculated on the dry weight of the fabric) is dried at I00 andthen fixed for 60 seconds at a temperature of 210. The dyed goods arerinsed with water, soaped and dried. Under these conditions a greendyeing is obtained which is fast to washing, light and sublimation.

We claim:

I l. A dyestuff free from salt-forming, water-solubilizing groups whichdissociate acid in water, which dyestutf is of the formula I O NH-Ri l CO-N N =N- Z wherein R, represents hydrogen or lower alkyl,

R represents hydrogen, lower alkyl, hydroxy-lower alltyl, alkenyl of atmost four carbon atoms. cyclohexyl or benzyl, and

R represents hydrogen, lower alkyl, hydroxy-lower alkyl or R and R takentogether with the nitrogen atom to which they are linked, representpyrrolidino, piperidino or morpholino,

Z represents phenyl or phenyl monosubstituted by chlorine, bromine,fluorine, nitro, lower alkyl, lower alkoxy, hydroxy-lower alkyl, loweralkoxy-carbonyl, lower alltylsulfonyl or lower alkyl-sulfonyloxy,

and ring A bears no further substituents or is further monosubstitutedby methyl, methoxy or chlorine.

2. A dyestuff as defined in claim I wherein each of R and R representshydrogen or lower alkyl, or R, and R, taken together 'with the nitrogenatom to which they are linked represent piperidino or morpholino.

3. A dyestuff as defined in claim 2 wherein each of R, and R representslower alkyl.

4. A dyestuff as defined in claim 3 wherein Z represents phenyl ormethylphenyl and ring A is without further substituents or is furthersubstituted by one methyl group.

5. A dyestuff as defined in claim 2 wherein each of R R; and R ishydrogen, Z is phenyl and ring A bears no further substituents.

6. A dyestuff as defined in claim 2 wherein R,is hydrogen,

represents morpholino, Z is phenyl and ring A bears no furthersubstituents.

7. A dyestuff as defined in claim 4 wherein R is hydrogen, each of R andR represents methyl, Z is phenyl and ring A bears no furthersubstituents.

8. A dyestufi' as defined in claim 4 wherein R, is hydrogen, each of Rand R represents ethyl, Z is phenyl and ring A bears no furthersubstituents.

i i i i

2. A dyestuff as defined in claim 1 wherein each of R3 and R4 representshydrogen or lower alkyl, or R3 and R4 taken together with the nitrogenatom to which they are linked represent piperidino or morpholino.
 3. Adyestuff as defined in claim 2 wherein each of R3 and R4 representslower alkyl.
 4. A dyestuff as defined in claim 3 wherein Z representsphenyl or methylphenyl and ring A is without further substituents or isfurther substituted by one methyl group.
 5. A dyestuff as defined inclaim 2 wherein each of R1, R3 and R4 is hydrogen, Z is phenyl and ringA bears no further substituents.
 6. A dyestuff as defined in claim 2wherein R1is hydrogen, represents morpholino, Z is phenyl and ring Abears no further substituents.
 7. A dyestuff as defined in claim 4wherein R1 is hydrogen, each of R3 and R4 represents methyl, Z is phenyland ring A bears no further substituents.
 8. A dyestuff as defined inclaim 4 wherein R1 is hydrogen, each of R3 and R4 represents ethyl, Z isphenyl and ring A bears no further substituents.